JP2002275008A - Hydantoin-stabilized composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition stabilized with a halogenated hydantoin compound and easy to handle. SOLUTION: This composition is a microbicidal composition that is obtained by dissolving a halogenated hydantoin compound of formula 1 (X and Y are each H or a halogen atom, wherein at least one of them is a halogen atom) as the active ingredient in a solvent consisting mainly of sulfolane and containing a halogen acid salt, wherein the halogenated hydantoin compound is 1-bromo-3-chloro-5,5-dimethyl hydantoin in particular. The method for stabilizing the halogenated haydantoin compound is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a pulp and paper industry for preventing the adhesion of slime derived from microorganisms such as bacteria and fungi in the paper making process, and for coating, latex, starch slurry and paper. Sterilization to prevent industrial water-based compositions made based on water such as coating colors, washing water, cooling water, adhesives, metalworking oils, etc. from undergoing spoilage, discoloration, and deterioration of physical properties due to microbial contamination. The present invention relates to a composition and a sterilization method.

2. Description of the Related Art In the papermaking process in the pulp and paper industry, a large amount of water is used for producing paper, and the water contains various kinds of water necessary for producing paper. Since organic matter is dispersed and dissolved, it is likely to be a nutrient source for microorganisms such as bacteria and fungi. Microorganisms such as bacteria and fungi proliferate based on these nutrients during the papermaking process, produce mucous metabolites, and take in the pulp, filler, and other papermaking raw materials that are dispersed during the papermaking process, Slime is formed on the wall or flow box inside the stagnant chest. The formed slime gradually increases and is gradually released and is incorporated into paper together with papermaking raw materials such as pulp and appears as foreign matter on paper, resulting in deterioration of quality. In recent years, since paper is made at a considerably high speed, in the worst case, the paper is cut off, causing a decrease in productivity. Also, industrial water-based compositions made based on water, such as paints, latex, and starch slurries, cause decay due to contamination by bacteria, resulting in odor generation, reduced viscosity, and deterioration of physical properties such as pH fluctuation. In addition, the strainer is clogged, colored, and foreign matters are mixed in due to propagation of fungi (filamentous fungi).

[0002] Various chemicals have been used as disinfectants to prevent the generation of slime due to microbial factors in the papermaking process. The same applies to fungicides for the purpose of preventing spoilage of various aqueous compositions. For example, in the papermaking process, 2,2-dibromo-
In addition to 3-nitrilopropionamide, 4,5-dichloro-1,2-dithiol-3-one, methylenebisthiocyanate, 1,4-bis (bromoacetoxy) -2-butene or 1,2 having excellent bacteriostatic power -Bis (bromoacetoxy) ethane and the like are often used. 5-Chloro-2-methyl-4, which is excellent in bacteriostatic activity and excellent in stability in aqueous compositions for preventing decay of aqueous compositions.
-Isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane-1,3-diol and the like are often used. .

[0003] Among these fungicides, halogenated hydantoin compounds are one of the excellent ones, and 1-bromo-3-chloro-5,5-dimethylhydantoin is known as a slime control agent. However, these hydantoin compounds have poor stability, and when they are dissolved in a solvent to form a liquid, they rapidly decompose, making it practically very difficult to put them into practical use. Therefore, when these are added, for example, in the paper making process, they need to be added in powder form. When the powder is added in a state of powder, it is very difficult to handle, and a special device for adding the powder is required, resulting in a very high cost. In addition, the powder may block due to moisture in the system, and troubles that cannot be added normally may frequently occur. JP-A-4-59707 proposes a composition containing this hydantoin compound and an isothiazoline compound. However, this composition has very poor stability, and no example of a stable formulation is given. Thus, the use of these combinations of compositions required the separate addition of drugs into the system. JP-A-10-101511 proposes a composition containing this hydantoin compound and dibromonitrilopropionamide. As an example containing these components, there is disclosed one using dimethylformamide and esters as a solvent. However, these preparations have insufficient stability and are not practical in that dimethylformamide, which has a safety problem, is used.

[0004]

Means for Solving the Problems The present inventor has made intensive studies to improve the above-mentioned drawbacks, and as a result, found that the above-mentioned drawbacks were improved, and completed the present invention. That is, the present invention relates to the general formula (1) (Wherein X and Y are the same or different and represent hydrogen or halogen, and at least one of X or Y represents halogen), wherein at least one halogenated hydantoin compound represented by the following formula is used as an active ingredient, and sulfolane or sulfolane is added thereto. A method for stabilizing a halogenated hydantoin compound, comprising dissolving in a disinfectant composition using a solvent as a main component, a halide as a stabilizer and sulfolane or a solvent mainly as sulfolane.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The hydantoin compound used in the present invention is a fungicidal and fungicidal substance, wherein X and Y in the above formula (1) are the same or different and represent hydrogen or halogen.
Halogen includes chlorine, bromine and iodine, and chlorine or bromine is preferred from the viewpoint of bactericidal activity and fungicidal activity. Representative examples thereof include 1-bromo-3-chloro-5,5-dimethylhydantoin and 1,3-dibromo-
5,5-dimethylhydantoin, 1,3-dichloro-
5,5-dimethylhydantoin can be used, and one or a mixture of two or more of these can be used in the sterilizing composition.

The sulfolane used in the fungicidal composition of the present invention can be used alone or in admixture with another solvent which does not affect the solubility and stability of the halogenated hydantoin compound or sulfolane. No problem. Although the solvent is not particularly limited, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol,
Acetic acid, propionic acid, acetone, dimethylacetamide, dimethylsulfoxide, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, water-soluble solvents such as γ-butyrolactone, dimethylnaphthalene, dodecylbenzene, liquid paraffin, isophorone,
A lipophilic solvent such as kerosene, dibutyl adipate, diethyl phthalate, diethylene glycol monobutyl ether acetate, propylene carbonate, coconut oil, rapeseed oil, cottonseed oil, castor oil, and soybean oil can be used as appropriate. These water-soluble solvents and lipophilic solvents may be used alone or in combination of two or more.

Further, in the germicidal composition of the present invention, it may be mixed with a surfactant or other additives to such an extent that the solubility and stability of the halogenated hydantoin compound are not affected. As surfactants, nonionic surfactants, anionic surfactants, cationic surfactants,
Zwitterionic surfactants and the like can be used. Although these surfactants are not particularly limited, examples of nonionic surfactants include polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Fatty acid esters and the like, and anionic surfactants include alkylbenzene sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, dialkyl succinate sulfate, and the like. Examples of the agent include an aliphatic amine salt and a quaternary ammonium salt thereof, and examples of the amphoteric surfactant include a betaine-type surfactant and an aminocarboxylate. In addition, these nonionic surfactants,
The anionic surfactant, the cationic surfactant, and the amphoteric surfactant may be used alone or in combination of two or more. If necessary, a chelating agent, a rust inhibitor, a scale inhibitor, and the like can be added.

The halogenated hydantoin compound represented by the above general formula (1) in the halogenated hydantoin stabilized composition of the present invention is preferably contained in an amount of 0.5 to 50% by weight. % By weight. Further, the sulfolane used in the present invention is preferably contained so as to be 20 to 99% by weight in the sterilizing composition,
More preferably, it is 50 to 90%.

The halogenate used in the present invention is ABO
n (A is an alkali metal, B is chlorine, bromine or iodine,
n is an integer of 1 to 4), and the alkali metal is not particularly limited, but usually a sodium salt or a potassium salt is used. Examples of these include sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate, potassium chlorate, potassium perchlorate, sodium bromate, potassium bromate, sodium iodate, potassium iodate. And sodium periodate, potassium periodate and the like, and sodium bromate, sodium iodate and sodium periodate are preferred. The content of the halogen salt is usually from 0 to 10% by weight, more preferably from 0.1 to 2% by weight.

[0010]

EXAMPLES Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
All the compounding ratios shown below are% by weight. In addition, the germicidal composition of each example was prepared by ordinary stirring at room temperature at a ratio indicated for each component shown in each example.

[0011]

Examples 1 to 7 and Comparative Examples 1 to 7 Halogenated hydantoin compounds were formulated in the formulations shown in Tables 1 and 2 to obtain germicidal compositions. The halogenated hydantoin compounds in the table are represented by the following abbreviations. A stability test and a slime adherence prevention effect confirmation test were performed on these sterilizing compositions.

1,3-dichloro-5,5-dimethylhydantoin: DCDH 1,3-dibromo-5,5-dimethylhydantoin:
DBDH 1-bromo-3-chloro-5,5-dimethylhydantoin: BCDH

[0013]

[Table 1] Examples

[0014]

[Table 2] Comparative example MDG: diethylene glycol monomethyl ether DMAC: dimethylacetamide

[0015]

[Test Example 1] Temporal stability test The sterilizing compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were subjected to 45 ° C.
And the content of the halogenated hydantoin compound was analyzed at regular intervals using high performance liquid chromatography. The survival rate was expressed as a percentage. Table 3 shows the results.

[0016]

[Table 3] Result of aging test (45 ° C)

[0017]

[Test Example 2] Test for confirming the effect of preventing slime adhesion with white water in the papermaking process White paperboard papermaking water collected from a papermaking company was 2 cm x 10
0.5 ml / min was poured into a 100 ml container immersed with a 16-mesh 16 g mesh wire and overflowed. The liquid temperature was kept at 30 ° C., and 25 μl of a drug (Examples 3, 5 and Comparative Examples 3, 7) stored at 45 ° C. for 7 days was added every 8 hours, and the operation was continued for 5 days. The slime attached to the wire mesh was investigated. The slime adhesion rate was expressed as a percentage of the area of the slime adhering to the wire mesh.

[0018]

[Table 4] Slime adhesion prevention test results in papermaking process white water

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Claims (4)

[Claims] 1. General formula (1) (Wherein X and Y are the same or different and represent hydrogen or halogen, and at least one of X or Y represents halogen), wherein at least one halogenated hydantoin compound represented by the following formula is used as an active ingredient, and sulfolane or sulfolane is added thereto. A bactericidal composition containing a solvent as a main component. 2. General formula (1) (Wherein X and Y are the same or different and represent hydrogen or halogen, and at least one of X or Y represents halogen), wherein at least one halogenated hydantoin compound represented by the following formula is used as an active ingredient, and sulfolane or sulfolane is added thereto. 2. The disinfecting composition according to claim 1, which contains a solvent as a main component and further contains a halide. 3. The fungicidal composition according to claim 1, wherein the halogenated hydantoin compound is 1-bromo-3-chloro-5,5-dimethylhydantoin. 4. General formula (1) (Wherein X and Y are the same or different and each represent hydrogen or halogen, and at least one of X and Y represents halogen), wherein the halogenated hydantoin compound is dissolved in sulfolane or a solvent mainly containing sulfolane. Characterizing method of stabilizing sterilizing composition